(η1-piperidine) pentacarbonyl molybdenum(0) | 19456-57-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (η1-piperidine) pentacarbonyl molybdenum(0)
• 英文别名: piperidine-pentacarbonylmolybdenum(0)；(piperidine)molybdenum pentacarbonyl；[molybdenum(pentacarbonyl)(C5H10NH)]；Carbon monoxide;molybdenum;piperidine
• CAS: 19456-57-6
• 化学式: C₁₀H₁₁MoNO₅
• 分子量: 321.141
• InChiKey: OYDFBRFYGGTBEV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.57
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  17
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (η1-piperidine) pentacarbonyl molybdenum(0) 在 三苯基膦 作用下， 以 正己烷 为溶剂， 生成 triphenylphosphinemolybdenumpentacarbonyl
  参考文献：
  名称：

  Kinetic studies of ligand substitution reactions and general-base catalysis in amine-ligand exchange processes for Group 6B metal carbonyl amine derivatives. Kinetic and spectroscopic evidence for hydrogen-bonded intermediates

  摘要：

  DOI：

  10.1021/ic50226a029
• 作为产物：
  描述：

  cis-tetracarbonylbis(piperidine)molybdenum 在 一氧化碳 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 (η1-piperidine) pentacarbonyl molybdenum(0)
  参考文献：
  名称：

  Ligand effects in the substitution chemistry of cis-bis(piperidine)tetracarbonylmolybdenum(O). A molybdenum-95 NMR study

  摘要：

  Molybdenum-95 NMR chemical shifts are reported for a series of Mo(O) compounds of the type Mo(CO)4(pip)(2-n)L(n) (n = 1, 2; L = substituted pyridine ligands). The delta(Mo-95) values correlate well with the pK(a) values for the substituted pyridines; for the n = 1 series, delta(Mo-95) ranges from - 1053 ppm (pK(a) = 1.86 for (CN) to - 1120 ppm (pK(a) = 9.61 for 4-NMe2). The effects of solvent polarity and some in situ reactivity studies are described and the nature of the Mo-L bond compared to that with piperidine and some other ligands is discussed.

  DOI：

  10.1016/0584-8539(92)80084-a

文献信息

• Intramolecular exchange of coordinated and dangling phosphines in pentacarbonyl group 6 complexes of 1,1,2-tris(diphenylphosphino)ethane
  作者：Richard L. Keiter、Ping Ye、Ellen A. Keiter、John William Benson、Weiying Lin、Douglas E. Brandt、Joel S. Southern、Arnold L. Rheingold、Ilia Guzei、Kraig A. Wheeler、Lew W. Cary

  DOI：10.1016/j.ica.2010.08.039

  日期：2010.12

  activation for 1Cr ⇌ 2Cr and 1W ⇌ 2W are 119.0 and 92.6 kJ mol −1 , respectively, and entropies of activation are 1.4 and −28.2 J K −1 mol −1 , respectively. Isomerization is 10 4 times faster for these complexes than for (OC) 5 M[κ 1 -PPh 2 CH 2 CH 2 P( p -tolyl) 2 ]. A novel mechanism is proposed to account for the rate differences. The X-ray crystal structure of 2W shows that the phosphorus atom of the

  连接异构体（OC）5 M [κ1 -PPh 2 CH 2 CH（PPh 2）2] 1和（OC）5 M [κ1 -PPh 2 CH（PPh 2）CH 2 PPh 2] 2（M = Cr，Mo和W在室温下平衡存在。CDCl 3中在25°C下1Cr Cr 2Cr，1Mo⇌2Mo和1W⇌2W的平衡常数分别为2.61、5.0和4.74。焓有利于正向反应（分别为ΔH = -13.5，−12和-12.2 kJ mol -1），而熵有利于逆反应（分别为ΔS = −37.6，−28和-28.2 JK -1 mol -1）。 ）。异构化比螯合1Mo≫ 2Mo≫ 1W lation 2W> 1Cr⇌2Cr快得多。1Cr⇌2Cr和1W⇌2W的活化焓分别为119.0和92.6 kJ mol -1，活化熵分别为1.4和-28.2 J K -1 mol -1。这些配合物的异构化速度比（OC）5 M [κ1 -PPh 2
• Halogen oxidation of some group VI metal carbonyl derivatives
  作者：S.C. Tripathi、S.C. Srivastava、A.K. Shrimal

  DOI：10.1016/s0020-1693(00)95609-3

  日期：1976.1

  Halogen oxidation of several amine chromium and amine molybdenum carbonyls has been studied. The species isolated were Cr(CO)3(amine)X2, Mo(CO)4 (amine)X2, Mo(CO)3(amine)2X2, Mo(CO)2(amine)2X2 and [Mo(CO)3(amine)3X]X (X = halogen). (1-Diphenylphosphino-2-diphenylarsinoethane)metal tetracarbonyls (metal = Cr, Mo, W) after reaction with halogens gave [Cr(CO)4(1-diphenylphosphino-2-diphenylarsinoethane)I]I

  已经研究了几种胺铬和胺钼羰基的卤素氧化。分离出的物种是Cr（CO）3（胺）X 2，Mo（CO）4（胺）X 2，Mo（CO）3（胺）2 X 2，Mo（CO）2（胺）2 X 2和[Mo（CO）3（胺）3 X] X（X =卤素）。与卤素反应后的（1-二苯基膦基-2-二苯基ar氨基乙烷）金属四羰基化合物（金属= Cr，Mo，W）得到[Cr（CO）4（1-二苯基膦基-2-二苯基ar氨基乙烷）I] I，M（CO）3（ 1-二苯基膦基-2-二苯基ar基乙烷）X 2（M ＝ Mo，W； X ＝ Br，I）和M（CO）2（1-二苯基膦基-2-二苯基ar氨基乙烷）Cl 2（M ＝ Mo，W）。配合物已经通过微分析，红外光谱和电导率测量进行了鉴定。
• Electrochemistry and [60]fullerene displacement reactions of (dihapto-[60]fullerene) pentacarbonyl metal(<scp>0</scp>) (M = Cr, Mo, W)
  作者：Elvin Igartúa-Nieves、Yessenia Ocasio-Delgado、María D. L. A. Torres-Castillo、Omar Rivera-Betancourt、José A. Rivera-Pagán、Diana Rodriguez、Gustavo E. López、José E. Cortés-Figueroa

  DOI：10.1039/b618260g

  日期：——

  Cyclic voltammetry (CV) measurements on (η2-C60)M(CO)5 complexes (M = Cr, Mo, W) in dichloromethane show three [60]fullerene-centered and reversible reduction/oxidation waves. The E1/2 values of these waves are shifted to positive values relative to the corresponding values of the uncoordinated [60]fullerene in the same solvent. A Jahn–Teller type distortion of the spherical surface of [60]fullerene promoted by [60]fullerene–metal π-backbonding may explain the observed positive shifts. Lewis bases (L = piperidine and triphenyl phosphine) displace [60]fullerene from (η2-C60)M(CO)5 complexes. Analysis of the activation parameters for the metal–[60]fullerene dissociation, the metal–[60]fullerene bond enthalpies (from DFT computations), and metal–solvent (benzene) bond enthalpies (from DFT computations) suggests appreciable solvent contribution to the transition state leading to formation of the intermediate species solvent–M(CO)5. Appreciable transition state stabilization due to solvation of the intermediate species is inferred for M = Mo and W. For M = Cr, stabilization of the intermediate species due to solvation is not accompanied by the corresponding transition state stabilization.

  在二氯甲烷中对 (η2-C60)M(CO)5 复合物（M = Cr、Mo、W）进行的循环伏安（CV）测量显示出三个以 [60] 富勒烯为中心的可逆还原/氧化波。与同一溶剂中未配位的 [60] 富勒烯的相应值相比，这些波的 E1/2 值偏向正值。[60]富勒烯的球形表面在[60]富勒烯-金属 π 反键作用的促进下发生了贾恩-泰勒（Jahn-Teller）型畸变，这可以解释所观察到的正偏移。路易斯碱（L = 哌啶和三苯基膦）将[60]富勒烯从 (η2-C60)M(CO)5 复合物中置换出来。对金属-[60]富勒烯解离的活化参数、金属-[60]富勒烯键焓（来自 DFT 计算）和金属-溶剂（苯）键焓（来自 DFT 计算）的分析表明，溶剂对过渡态有明显的贡献，导致形成中间物种溶剂-M(CO)5。对于 M = Mo 和 W，由于中间产物的溶解，可以推断出明显的过渡态稳定。对于 M = Cr，由于溶解而导致的中间产物稳定并没有伴随相应的过渡态稳定。
• Photoacoustic Calorimetry and Quantum Yields of Mo(CO)₆ Ligand Exchange in Linear Alkanes:  Determination of Volume of Reaction, Energetics, and Kinetics of Nucleophile Displacement of Alkane from Mo(CO)₅(Alkane)
  作者：Tianjie Jiao、Ging-Long Leu、Gerard J. Farrell、Theodore J. Burkey

  DOI：10.1021/ja003165g

  日期：2001.5.1

  of linear alkanes. The enthalpies for substitution of CO on Mo(CO)(6) by an alkane and of coordinated alkane on Mo(CO)(5)(alkane) by THF are 30 and -14 kcal/mol, respectively. Likewise, the volumes of reaction are 18 and -1 mL/mol. From available data for the Mo--CO bond energy, these results allow the calculation of the Mo-alkane and Mo-THF bond energies (11 and 25 kcal/mol, respectively). The Mo-alkane

  光声量热法 (PAC) 和光度计研究用于确定生产瞬态中间体 Mo(CO)(5)-烷烃的焓和反应体积，以及随后与四氢呋喃 (THF) 的反应。焓和反应体积都对光声信号有贡献，并且已经通过使用一系列线性烷烃改变溶剂热膨胀特性来解决。烷烃取代 Mo(CO)(6) 上的 CO 和 THF 取代 Mo(CO)(5)(烷烃) 上的配位烷烃的焓分别为 30 和 -14 kcal/mol。同样，反应体积为 18 和 -1 mL/mol。根据 Mo-CO 键能的可用数据，这些结果允许计算 Mo-烷烃和 Mo-THF 键能（分别为 11 和 25 kcal/mol）。Mo-烷烃的结果比我们之前的 PAC 研究少 7 kcal/mol，该研究忽略了反应体积，与动力学研究的结果更加吻合。每一步反应体积的巨大绝​​对差异部分归因于在 Mo--THF 键形成过程中产生的空隙体积。通常，在计算 PAC 研究配体取代焓时不能忽略反应体积。与
• Tripathi, S. C.; Srivastava, S. C.; Srivastava, P. K., Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 1983, vol. 22, # 4, p. 350 - 352
  作者：Tripathi, S. C.、Srivastava, S. C.、Srivastava, P. K.

  DOI：——

  日期：——